This invention relates to electrophoretic particles (i.e., particles for use in an electrophoretic medium) and processes for the production of such electrophoretic particles. This invention also relates to electrophoretic media and displays incorporating such particles. More specifically, this invention relates to novel black or dark colored electrophoretic particles.
Particle-based electrophoretic displays, in which a plurality of charged particles move through a suspending fluid under the influence of an electric field, have been the subject of intense research and development for a number of years. Such displays can have attributes of good brightness and contrast, wide viewing angles, state bistability, and low power consumption when compared with liquid crystal displays.
The terms “bistable” and “bistability” are used herein in their conventional meaning in the art to refer to displays comprising display elements having first and second display states differing in at least one optical property, and such that after any given element has been driven, by means of an addressing pulse of finite duration, to assume either its first or second display state, after the addressing pulse has terminated, that state will persist for at least several times, for example at least four times, the minimum duration of the addressing pulse required to change the state of the display element. The optical property is typically color perceptible to the human eye, but may be another optical property, such as optical transmission, reflectance, luminescence or, in the case of displays intended for machine reading, pseudo-color in the sense of a change in reflectance of electromagnetic wavelengths outside the visible range. It is shown in the U.S. Published application No. 2002/0180687 that some particle-based electrophoretic displays capable of gray scale are stable not only in their extreme black and white states but also in their intermediate gray states, and the same is true of some other types of electro-optic displays. This type of display is properly called “multi-stable” rather than bistable, although for convenience the term “bistable” may be used herein to cover both bistable and multi-stable displays.
Nevertheless, problems with the long-term image quality of electrophoretic displays have prevented their widespread usage. For example, particles that make up electrophoretic displays tend to settle, resulting in inadequate service-life for these displays.
Numerous patents and applications assigned to or in the names of the Massachusetts Institute of Technology (MIT) and E Ink Corporation have recently been published describing encapsulated electrophoretic media. Such encapsulated media comprise numerous small capsules, each of which itself comprises an internal phase containing electrophoretically-mobile particles suspended in a liquid suspension medium, and a capsule wall surrounding the internal phase. Typically, the capsules are themselves held within a polymeric binder to form a coherent layer positioned between two electrodes. Encapsulated media of this type are described, for example, in U.S. Pat. Nos. 5,930,026; 5,961,804; 6,017,584; 6,067,185; 6,118,426; 6,120,588; 6,120,839; 6,124,851; 6,130,773; 6,130,774; 6,172,798; 6,177,921; 6,232,950; 6,249,271; 6,252,564; 6,262,706; 6,262,833; 6,300,932; 6,312,304; 6,312,971; 6,323,989; 6,327,072; 6,376,828; 6,377,387; 6,392,785; 6,392,786; 6,413,790; 6,422,687; 6,445,374; 6,445,489; 6,459,418; 6,473,072; 6,480,182; 6,498,114; 6,504,524; 6,506,438; 6,512,354; 6,515,649; 6,518,949; 6,521,489; 6,531,997; 6,535,197; 6,538,801; 6,545,291; 6,580,545; 6,639,578; 6,652,075; 6,657,772; 6,664,944 and 6,680,725; and U.S. Patent applications Publication Nos. 2002/0019081; 2002/0021270; 2002/0053900; 2002/0060321; 2002/0063661; 2002/0063677; 2002/0090980; 2002/0106847; 2002/0113770; 2002/0130832; 2002/0131147; 2002/0145792; 2002/0171910; 2002/0180687; 2002/0180688; 2002/0185378; 2003/0011560; 2003/0011868; 2003/0020844; 2003/0025855; 2003/0034949; 2003/0038755; 2003/0053189; 2003/0076573; 2003/0096113; 2003/0102858; 2003/0132908; 2003/0137521; 2003/0137717; 2003/0151702; 2003/0189749; 2003/0214695; 2003/0214697 and 2003/0222315; and International applications Publication Nos. WO 99/67678; WO 00/05704; WO 00/38000; WO 00/38001; WO 00/36560; WO 00/67110; WO 00/67327; WO 01/07961; WO 01/08241; and WO 03/104884.
Known electrophoretic media, both encapsulated and unencapsulated, can be divided into two main types, referred to hereinafter for convenience as “single particle” and “dual particle” respectively. A single particle medium has only a single type of electrophoretic particle suspended in a suspending medium, at least one optical characteristic of which differs from that of the particles. (In referring to a single type of particle, we do not imply that all particles of the type are absolutely identical. For example, provided that all particles of the type possess substantially the same optical characteristic and a charge of the same polarity, considerable variation in parameters such as particle size and electrophoretic mobility can be tolerated without affecting the utility of the medium.) When such a medium is placed between a pair of electrodes, at least one of which is transparent, depending upon the relative potentials of the two electrodes, the medium can display the optical characteristic of the particles (when the particles are adjacent the electrode closer to the observer, hereinafter called the “front” electrode) or the optical characteristic of the suspending medium (when the particles are adjacent the electrode remote from the observer, hereinafter called the “rear” electrode (so that the particles are hidden by the suspending medium).
A dual particle medium has two different types of particles differing in at least one optical characteristic and a suspending fluid which may be uncolored or colored, but which is typically uncolored. The two types of particles differ in electrophoretic mobility; this difference in mobility may be in polarity (this type may hereinafter be referred to as an “opposite charge dual particle” medium) and/or magnitude. When such a dual particle medium is placed between the aforementioned pair of electrodes, depending upon the relative potentials of the two electrodes, the medium can display the optical characteristic of either set of particles, although the exact manner in which this is achieved differs depending upon whether the difference in mobility is in polarity or only in magnitude. For ease of illustration, consider an electrophoretic medium in which one type of particles is black and the other type white. If the two types of particles differ in polarity (if, for example, the black particles are positively charged and the white particles negatively charged), the particles will be attracted to the two different electrodes, so that if, for example, the front electrode is negative relative to the rear electrode, the black particles will be attracted to the front electrode and the white particles to the rear electrode, so that the medium will appear black to the observer. Conversely, if the front electrode is positive relative to the rear electrode, the white particles will be attracted to the front electrode and the black particles to the rear electrode, so that the medium will appear white to the observer.
If the two types of particles have charges of the same polarity, but differ in electrophoretic mobility (this type of medium may hereinafter to referred to as a “same polarity dual particle” medium), both types of particles will be attracted to the same electrode, but one type will reach the electrode before the other, so that the type facing the observer differs depending upon the electrode to which the particles are attracted. For example suppose the previous illustration is modified so that both the black and white particles are positively charged, but the black particles have the higher electrophoretic mobility. If now the front electrode is negative relative to the rear electrode, both the black and white particles will be attracted to the front electrode, but the black particles, because of their higher mobility will reach it first, so that a layer of black particles will coat the front electrode and the medium will appear black to the observer. Conversely, if the front electrode is positive relative to the rear electrode, both the black and white particles will be attracted to the rear electrode, but the black particles, because of their higher mobility will reach it first, so that a layer of black particles will coat the rear electrode, leaving a layer of white particles remote from the rear electrode and facing the observer, so that the medium will appear white to the observer: note that this type of dual particle medium requires that the suspending fluid be sufficiently transparent to allow the layer of white particles remote from the rear electrode to be readily visible to the observer. Typically, the suspending fluid in such a display is not colored at all, but some color may be incorporated for the purpose of correcting any undesirable tint in the white particles seen therethrough.
Both single and dual particle electrophoretic displays may be capable of intermediate gray states having optical characteristics intermediate the two extreme optical states already described.
Some of the aforementioned patents and published applications disclose encapsulated electrophoretic media having three or more different types of particles within each capsule. For purposes of the present application, such multi-particle media are regarded as sub-species of dual particle media.
Also, many of the aforementioned patents and applications recognize that the walls surrounding the discrete microcapsules in an encapsulated electrophoretic medium could be replaced by a continuous phase, thus producing a so-called polymer-dispersed electrophoretic display, in which the electrophoretic medium comprises a plurality of discrete droplets of an electrophoretic fluid and a continuous phase of a polymeric material, and that the discrete droplets of electrophoretic fluid within such a polymer-dispersed electrophoretic display may be regarded as capsules or microcapsules even though no discrete capsule membrane is associated with each individual droplet; see for example, the aforementioned 2002/0131147. Accordingly, for purposes of the present application, such polymer-dispersed electrophoretic media are regarded as sub-species of encapsulated electrophoretic media.
A related type of electrophoretic display is a so-called “microcell electrophoretic display”. In a microcell electrophoretic display, the charged particles and the suspending fluid are not encapsulated within microcapsules but instead are retained within a plurality of cavities formed within a carrier medium, typically a polymeric film. See, for example, International Application Publication No. WO 02/01281, and published U.S. application No. 2002/0075556, both assigned to Sipix Imaging, Inc.
Although electrophoretic media are often opaque (since, for example, in many electrophoretic media, the particles substantially block transmission of visible light through the display) and operate in a reflective mode, many electrophoretic displays can be made to operate in a so-called “shutter mode” in which one display state is substantially opaque and one is light-transmissive. See, for example, the aforementioned U.S. Pat. Nos. 6,130,774 and 6,172,798, and U.S. Pat. Nos. 5,872,552; 6,144,361; 6,271,823; 6,225,971; and 6,184,856. Dielectrophoretic displays, which are similar to electrophoretic displays but rely upon variations in electric field strength, can operate in a similar mode; see U.S. Pat. No. 4,418,346.
An encapsulated or microcell electrophoretic display typically does not suffer from the clustering and settling failure mode of traditional electrophoretic devices and provides further advantages, such as the ability to print or coat the display on a wide variety of flexible and rigid substrates. (Use of the word “printing” is intended to include all forms of printing and coating, including, but without limitation: pre-metered coatings such as patch die coating, slot or extrusion coating, slide or cascade coating, curtain coating; roll coating such as knife over roll coating, forward and reverse roll coating; gravure coating; dip coating; spray coating; meniscus coating; spin coating; brush coating; air knife coating; silk screen printing processes; electrostatic printing processes; thermal printing processes; inkjet printing processes; and other similar techniques.) Thus, the resulting display can be flexible. Further, because the display medium can be printed (using a variety of methods), the display itself can be made inexpensively.
However, the electro-optical properties of encapsulated electrophoretic displays could still be improved. Among the remaining problems of encapsulated electrophoretic displays are so-called “rapid white state degradation”, a relatively rapid decline in the reflectivity of the white optical state of the display during the first few days of operation. Another problem, which is discussed in detail in the aforementioned 2003/0137521 and WO 03/107315, is so-called “dwell state dependency”, which causes the change in optical state of an electrophoretic medium produced by a specific waveform to vary depending upon the time for which the electrophoretic medium has been in a particular optical state before the waveform is applied. Finally, it is advisable to make the white optical state of the display whiter and the black optical state darker.
As discussed in the aforementioned E Ink and MIT patents and applications, the presently preferred form of electrophoretic medium comprises white titania and carbon black particles in a hydrocarbon suspending fluid, this hydrocarbon being used alone or in admixture with a chlorinated hydrocarbon or other low dielectric constant fluid. Most other prior art electrophoretic displays which require a black pigment have also used carbon black for this purpose, apparently largely because the material is readily available in mass quantities and very inexpensive. However, the present inventors and their co-workers have discovered that the aforementioned problems with prior art electrophoretic displays are associated with the use of carbon black for the black electrophoretic particles. Carbon black has a complex and poorly understood surface chemistry, which may vary widely with the specific raw material (typically petroleum) and the exact process used for the carbon black production. Carbon black pigment particles also have a poorly understood aggregate, fractal structure. Furthermore, carbon black is notoriously effective in adsorbing gases and liquids with which it comes into contact, and such adsorbed gases and liquids can change the physicochemical properties of the carbon black surface. Hence, it is difficult to ensure consistent surface properties of carbon black from batch to batch. This is especially problematic in electrophoretic displays, since the electrophoretic particles used are typically so small (of the order of 1 μm) that their properties are dominated by the properties of their surfaces.
It has also been discovered (although this information is not disclosed in the prior art) that carbon black presents certain peculiar difficulties in obtaining proper charging of particles in opposite charge dual particle electrophoretic displays. Specifically, it has been found that when using carbon black and titania as the black and white particles respectively in an opposite charge dual particle electrophoretic display, combinations of charging agents and other materials which produce all positively charged carbon black particles tend to produce a minor proportion of titania particles which are also positively charged. The resultant mixture of negatively and positively charged titania particles leads to contamination of the extreme optical states of the medium, thus adversely affecting its contrast ratio.
Carbon black also has a low density. While this does not affect the operation of the display itself, it does complicate the manufacture of encapsulated dual particle displays. For reasons explained in several of the aforementioned E Ink and MIT patents, it is desirable that an encapsulated electrophoretic medium comprises a single, substantially close-packed layer of capsules. Also, when such an electrophoretic medium is produced by coating capsules on to a substrate, it is desirable that the exposed surface of the capsule layer be reasonably flat, since otherwise difficulties may be encountered in laminating the capsule layer to other layers in the final display. Production of such a substantially close-packed layer with a reasonably flat exposed surface is best achieved by coating capsules which are of substantially the same size. However, the encapsulation processes described in aforementioned E Ink and MIT patents produce capsules having a broad range of sizes, and hence it is necessary to separate out the capsules having the desired range of sizes. Many useful processes for sorting capsules by size rely upon using the density difference between the capsules and a surrounding medium to effect the desired sorting. The low density of carbon black, coupled with the small concentration at which it is used in most electrophoretic media, lead to capsule densities close to that of water, hindering the sorting process.
There is thus a need for a black particle for use in electrophoretic media that does not suffer from the problems associated with the use of carbon black. However, the search for such a black particle is subject to considerable difficulties. Although the optical properties of numerous pigments are of course known from their use in the paint and similar industries, a pigment for use in an electrophoretic display must possess several properties in addition to appropriate optical properties. The pigment must be compatible with the numerous other components of the electrophoretic medium, including the suspending fluid, any other pigment particles present, charge control agents and surfactants typically present in the suspending fluid, and the capsule wall material (if a capsule wall is present). The pigment particles must also be able to sustain a charge when suspended in the suspending fluid, and the zeta potentials of the particles caused by such charges should all be of the same polarity and should not extend over an excessively wide range, or the electrophoretic medium may not have desirable electro-optic properties; for example, if some particles have very low zeta potentials, a very long driving pulse may be required to move such particles to a desired position within the electrophoretic medium, resulting in slow switching of the medium. It will be appreciated that such information relating to the ability of pigment particles to acquire and hold charges is not available for most pigments potentially usable in an electrophoretic display, since such electrical properties are irrelevant to the normal commercial uses of the pigments.
The aforementioned copending application Ser. No. 09/140,846 mentions numerous pigments that are potentially useful in an electrophoretic display. It has now been found that one of these pigment, namely copper chromite (Cu2Cr2O3) has particular advantages for use in electrophoretic media and displays, and this invention relates to electrophoretic media and displays containing copper chromite. It has also been found that certain surface treatments, in particular the formation of layers of silica and formation of polymers attached to the copper chromite particle, substantially as described in the aforementioned copending applications Ser. Nos. 10/063,803 and 60/481,572, improve the performance of the copper chromite particle in electrophoretic media and displays, and this invention also relates to such modified copper chromite particles and electrophoretic media and displays containing them.